EP0007931B1 - Rubber-modified terpolymers with improved heat distortion resistance - Google Patents
Rubber-modified terpolymers with improved heat distortion resistance Download PDFInfo
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- EP0007931B1 EP0007931B1 EP78300909A EP78300909A EP0007931B1 EP 0007931 B1 EP0007931 B1 EP 0007931B1 EP 78300909 A EP78300909 A EP 78300909A EP 78300909 A EP78300909 A EP 78300909A EP 0007931 B1 EP0007931 B1 EP 0007931B1
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- Prior art keywords
- rubber
- polymer
- weight
- methacrylate
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- 229920001897 terpolymer Polymers 0.000 title description 7
- 229920000642 polymer Polymers 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 46
- 229920001971 elastomer Polymers 0.000 claims description 38
- 239000005060 rubber Substances 0.000 claims description 38
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 20
- 229920002857 polybutadiene Polymers 0.000 claims description 11
- -1 alkyl methacrylate ester Chemical class 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 6
- 229920003246 polypentenamer Polymers 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 15
- 239000003381 stabilizer Substances 0.000 description 15
- 238000007792 addition Methods 0.000 description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 230000006872 improvement Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229920005669 high impact polystyrene Polymers 0.000 description 5
- 239000004797 high-impact polystyrene Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000005063 High cis polybutadiene Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- OMNYXCUDBQKCMU-UHFFFAOYSA-N 2,4-dichloro-1-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C(Cl)=C1 OMNYXCUDBQKCMU-UHFFFAOYSA-N 0.000 description 1
- SZSWKGVWJBZNIH-UHFFFAOYSA-N 2-chloro-1-ethenyl-4-methylbenzene Chemical compound CC1=CC=C(C=C)C(Cl)=C1 SZSWKGVWJBZNIH-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers
Definitions
- This invention relates to terpolymers and specifically to styrene/maleic anhydride/methacrylate copolymers having a rubber modifier incorporated therein.
- Rubber-modified styrenic polymers commonly referred to as HIPS are very tough and durable and have seen broad acceptance in a variety of uses such as appliance housings and the like.
- HIPS begins to soften and lose its dimensional integrity under stress at temperatures below those at which it would be required to operate for a number of significant applications.
- a rubber-modified styrenic terpolymer composition has now been discovered that produces a surprising improvement in the heat distortion temperature by comparison with HIPS making it suitable for a wide range of uses for which HIPS is disqualified.
- the incorporation of the methacrylate termonomer has the effect of raising the tensile strength and the gloss of the rubber modified polymer in a most advantageous manner making the polymeric product most attractive for a broad spectrum of applications.
- a polymeric composition comprising a rubber substrate polymer having a glass transition temperature below 0°C. grafted with a superstrate polymer and dispersed in a matrix polymer, the superstrate and matrix polymers each comprising a monoalkenyl aromatic monomer, an unsaturated dicarboxylic acid anhydride and a C, to C 3 alkyl methacrylate ester characterised in that there is present in the superstrate and matrix polymers from 45 to 83 percent by weight of the monoalkenyl aromatic monomer, from 15 to 35 percent by weight of the unsaturated dicarboxylic acid anhydride and from 2 to 20 percent by weight of the C, to C 3 alkyl methacrylate ester and that the amount of rubber in the composition, calculated as ungrafted substrate, is from 2 to 30 percent of the composition weight.
- a second advantage is that other physical properties such as multiaxial impact strength, tensile strength, elongation at fail and gloss of the polymer apparently increase with the amount of the methacrylate in the composition.
- the preferred polymer compositions within this range will depend largely on the properties desired. Generally, however, the polymers containing from 4 to 10% by weight of the methacrylate comonomer are preferred. This is because the heat distortion temperature, as is explained later, initially increases rapidly with methacrylate content to a broad peak between about 7 and 15% content and thereafter begins a gradual decline. Thus, roughly the same improvement is generally obtained at 7% as at 15% methacrylate content. Additionally, it is preferred to retain the thermal stability as high as possible so as to permit more flexibility in the application of forming processes to the polymers.
- the polymeric composition of the invention comprises a rubber substrate polymer having a glass transition temperature (Tg) below 0°C. grafted with a superstrate polymer and dispersed in a matrix polymer, the superstrate and the matrix polymers each comprising from 45 to 83% (preferably from 50 or 60 to 75%) by weight of a monoalkenyl aromatic monomer, from 15 to 35% (preferably 20-30%) by weight of an unsaturated dicarboxylic acid anhydride, and from 2 to 20% (preferably 4 to 10%) by weight of a C, to C 3 alkyl methacrylate ester, the amount of rubber in the composition, calculated as ungrafted substrate, being from 2 to 30% of the composition weight.
- Tg glass transition temperature
- the rubber substrate component of the polymeric composition can be selected from a wide range of alternatives including butadiene polymers and copolymers, particularly the so-called "high-cis" diene rubbers which contain at least 90% by weight of cis-1,4-polybutadiene units, polyisoprene, polychloroprene, polyacrylate rubbers, and ethylene/propylene/diene rubbers (EPDM), polypentenamer and ethylene/vinyl acetate rubbers.
- Copolymers of cyclopentene with a minor proportion of a non-cyclic ⁇ olefin such as for example a copolymer of 55 to 95% of cyclopentene with from 5 to 45% of ethylene are also useful.
- Rubbers which have a Tg below 0°C. and which may be grafted with the monomers used to produce the polymeric composition can readily be supplied by the skilled reader.
- the preferred rubbers have a Tg below about -30°C. and the most preferred are polybutadiene, particularly high-cis polybutadiene and copolymers of butadiene with up to 40% by weight of styrene or acrylonitrile comonomer.
- the monoalkenyl aromatic monomer is preferably styrene but styrene derivatives such as alphamethylstyrene, chlorostyrene, 2,4-dichlorostyrene and 2-chloro-4-methylstyrene may be substituted for styrene in whole or in part if desired.
- the unsaturated dicarboxylic acid anhydride is most preferably maleic anhydride though any of the homologues of mallic anhydride such as itaconic, citraconic and aconitic anhydrides can also be used.
- the polymeric composition further comprises a C, to C 3 alkyl ester of methacrylic acid.
- the methacrylic ester can bp methyl methacrylate, ethyl methacrylate or propyl methacrylate.
- the preferred copolymerizable monomer is methyl methacrylate.
- the polymeric composition is conveniently prepared by dissolving the rubber in a solution of the monoalkenyl aromatic component and the methacrylate ester in a suitable solvent, and then polymerizing the solution with the anhydride component in the manner described in, for example, U.S.P. 2,971,939, U.S.P. 3,336,267 and U.S.P. 3,919,354.
- a suitable polymerization schedule can be devised on the basis of the relative reactivities of the monomers.
- Typical schedules involve preparing an initial reaction mixture comprising a solvent, the bulk of the alkenyl aromatic monomers, a very small amount (or none) of the anhydride monomer and the major proportion of the methacrylate termonomer. The rubber is dissolved in this mixture and the balance of the monomers is added slowly during the polymerization.
- the amount of rubber substrate (ungrafted basis) in the polymeric composition, which includes the grafted superstrate and any matrix polymer present, is in the range from 2 to 30% by weight based on the weight of the polymeric composition. Preferably, however, the rubber substrate represents from 5 to 25% of the weight of the polymeric composition.
- antioxidant stabilizers for styrenic polymers is available but particularly satisfactory results can be obtained using 1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl]benzene and 2,2'-methylene-bis-(4-methyl-6-tert-butyl phenol)terethalate.
- the rubber component usually requires a different stabilizer such as a tris(alkylphenyl)phosphite though the prior art can supply others that would be effective.
- the total amount of stabilizer that may be used is not critical but up to 5% by weight based on the total composition is usually found to be adequate. In general 0.1 to 2% is the range chosen for practical advantage.
- the polymeric composition can contain other additives such as for example, additional ungrafted rubber components such as the so-called block rubbers and radial block rubbers, flame retardants, smoke suppressants, U.V. stabilizers, lubricants, antistatic additives, colorants and fillers.
- additional ungrafted rubber components such as the so-called block rubbers and radial block rubbers, flame retardants, smoke suppressants, U.V. stabilizers, lubricants, antistatic additives, colorants and fillers.
- Figure 1 represents a graph plotting the change in DTUL with methacrylate content. The results plotted are those set forth in Example 9.
- the polymer compositions are described on the basis of a combination of elemental analysis and titrimetric analysis techniques.
- the rubber concentration is determined on the basis of material balances in the polymer composition. Unless otherwise stated the rubber used was a medium-cis polybutadiene rubber available from Firestone Corp. under the trade name "Diene 55".
- the Examples illustrate the results of varying the amount of the methacrylate ester in the composition and the surprising advantages obtained by maintaining the level in the range of 2 to 20% by weight.
- the multiaxial impact strength is shown. This is commonly called the F.D.I. and is measured according to ASTM D-1709 on a sample 2.9 mm in thickness.
- the Izod impact strengths were measured using 3.2x12.7x63.5 mm unannealed compression molded samples, notched 2.54 mm.
- the DTUL values given are for 3.2x12.7x127 mm unannealed compression molded samples tested under a 18.6 kg/sq.cm. stress.
- Unannealed compression molded samples were chosen in preference to injection molded samples so as to eliminate the variations that occur in the preparation of injection molded samples which become partially oriented during the forming process.
- the choice of unannealed compression molded samples which are not oriented during formation eliminates, one result-affecting variable and makes the comparison more significant.
- Example 1 The process described below is that used in Example 1 but essentially the same process was used in the other Examples with the difference that the initial monomer charge and the late added charge were changed in accordance with a computer model based on monomer reactivities to obtain polymers of different compositions.
- Typical late addition schedules of specified polymers predicted on the basis of the model are shown in Table 1.
- An agitated resin kettle was charged with 316 g. of styrene, 32.6 g. of methylmethacrylate, 0.5 g. of trisnonylphenyl phosphite (a stabilizer for the rubber) and a solvent mixture consisting of 50 g. of methyl ethyl ketone (MEK) and 75 g. of toluene.
- MEK methyl ethyl ketone
- a solution of 0.6 g. of azobisisobutyronitrile (AIBN) and 3.2 g. of maleic anhydride in 30 ml. of MEK was prepared. 5 MI of this solution were added to the solution in the resin kettle and the rest was added at a rate of 3 ml/hour thereafter.
- AIBN azobisisobutyronitrile
- MEK MEK
- the reaction mixture was raised to 85°C. and maintained at that level while late addition of a solution of 97 g. of maleic anhydride and 15 g. of methyl methacrylate in 97 g. of MEK was begun. The late addition was continued over a 6-1/2 hour period. After addition was complete the reaction was held at the reaction temperature for a further hour before 0.5 g. of hydroquinone was added to short-stop the reaction.
- the polymer was then separated from the solvent and residual monomer, dried, blended with 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (antioxidant) and molded into samples for evaluation.
- Example 1-3 The results obtained in Examples 1-3 are set forth in Table II below.
- Polymer a) was obtained using a 65/25/10 target polymer addition schedule; polymers b) and c) used the 56.8/26.8/16.4 schedule.
- Example 5 The process described in Example 1 was followed except that the catalyst was changed from azobisisobutyronitrile to a mixture of tertiary butyl peroctoate and tertiary butyl peracetate. The results obtained are set forth in Table III below. Example 5 is for the sake of comparison and shows the results obtained in the absence of the methyl methacrylate component.
- Comparison of Examples 1 with 4 shows that using the peracetate catalyst it is possible to get comparable impact strengths while using a smaller amount of total rubber.
- Comparison of the RM-SMA with RM/S/MA/MMA shows the advantage of having the MMA present in terms both of DTUL, and percentage elongation at fail.
- This Example shows the advantages of RM-S/MA/MMA terpolymers over the corresponding RM-SMA polymers.
- compositions compared were as follows:
- compositions described in Table V below were made up using the following polymers.
- Example 7 is for the purposes of comparison with the polymer of the invention described in Example 8.
- polymer was prepared in the manner described in Example 1 except for the addition of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene as antioxidant and the use of the catalyst combination of Example 4.
- This Example shows the decrease in temperature at which thermal degradation begins with the increase of the methyl methacrylate content.
- compositions were tested: (A) without a stabilizer; (B) using '0.5% by weight of a 2,6-di- tertiary butyl- p-cresol stabilizer; and (C) using a mixture of 0.5% by weight of each of the stabilizer of (B) and 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.
- the polymer used in Example 11 was prepared as follows:
- the polymer was then separated from the solvent and the residual monomer removed by a conventional method.
- the isolated polymer was blended with any desired additives, such as stabilizers, and compression molded into samples for evaluation.
- compositions contained 0.3% by weight of 1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl]benzene as an antioxidant stabilizer.
- Examples 11-13 and 16 used high-cis rubber while Examples 14 and 15 (Comparative) used the medium-cis rubber described above.
- Each sample was placed in the barrel of a capillary rheometer maintained at a constant temperature and extruded after a given residence time.
- the matrix phase of the polymer was separated from the grafted rubber phase and was analyzed for its maleic anhydride content by a standard titrimetric technique.
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Description
- This invention relates to terpolymers and specifically to styrene/maleic anhydride/methacrylate copolymers having a rubber modifier incorporated therein.
- Rubber-modified styrenic polymers, commonly referred to as HIPS are very tough and durable and have seen broad acceptance in a variety of uses such as appliance housings and the like.
- However, HIPS begins to soften and lose its dimensional integrity under stress at temperatures below those at which it would be required to operate for a number of significant applications.
- A rubber-modified styrenic terpolymer composition has now been discovered that produces a surprising improvement in the heat distortion temperature by comparison with HIPS making it suitable for a wide range of uses for which HIPS is disqualified.
- The influence of maleic anhydride on the heat distortion temperature of a styrenic polymer is very well known in the art and methods of polymerizing styrene and maleic anhydride are described for example in U.S. Patents 2,971,939; 2,989,517; 3,336,267 and British Patent 1,234,395.
- It is also known that such styrene/maleic anhydride copolymers can be rubber-modified to produce tough copolymers, similar in morphology to conventional HIPS but with a distinctly higher heat distortion temperature. Such products are described for example in British Patent 1,452,141 and U.S. Patent 3,919,354. These patents also disclose the use of termonomers such as methyl methacrylate in such compositions.
- It has now been found that if a specified amount of a methacrylate monomer is incorporated in the polymer, a surprising further improvement in the heat distortion temperature of the polymer is obtained without significant sacrifice in other desirable properties. This improvement does not however, extend across the full range of compositions described in the art but appears to be confined to the narrow compositional range hereinbelow specified.
- Additionally it is found that the incorporation of the methacrylate termonomer has the effect of raising the tensile strength and the gloss of the rubber modified polymer in a most advantageous manner making the polymeric product most attractive for a broad spectrum of applications.
- According to the present invention there is provided a polymeric composition comprising a rubber substrate polymer having a glass transition temperature below 0°C. grafted with a superstrate polymer and dispersed in a matrix polymer, the superstrate and matrix polymers each comprising a monoalkenyl aromatic monomer, an unsaturated dicarboxylic acid anhydride and a C, to C3 alkyl methacrylate ester characterised in that there is present in the superstrate and matrix polymers from 45 to 83 percent by weight of the monoalkenyl aromatic monomer, from 15 to 35 percent by weight of the unsaturated dicarboxylic acid anhydride and from 2 to 20 percent by weight of the C, to C3 alkyl methacrylate ester and that the amount of rubber in the composition, calculated as ungrafted substrate, is from 2 to 30 percent of the composition weight.
- It has been found that the presence of the Cl-C3 alkyl methacrylate component has particularly surprising consequences and that the range described above which is mandated by a combination of factors, defines a group of novel rubber-modified terpolymers with unexpected and advantageous properties.
- It is found for example that the incorporation of the methacrylate comonomer increases the distortion temperature under load (DTUL) of the polymer. The effect of maleic anhydride on DTUL was known but it was not known however, that a further improvement can be obtained if a methacrylate comonomer is also present. However, this improvement is only obtained over a narrow range and above about 2096 by weight methacrylate in the polymer, the advantage is lost.
- A second advantage is that other physical properties such as multiaxial impact strength, tensile strength, elongation at fail and gloss of the polymer apparently increase with the amount of the methacrylate in the composition.
- The utility of the above advantages is however, circumscribed by the third factor which is that addition of a methacrylate comonomer is found to reduce the thermal decomposition temperature of the polymer. The effect of this can be controlled to some extent by addition of certain stabilizers but it is found that above about 20% by weight of the methacrylate comonomer it is not possible to obtain a polymer that is stable at its processing temperature for the length of time required for conventional forming processes.
- Thus, the interplay of these three factors defines in a totally unexpected fashion a range of rubber-modified terpolymers with very advantageous properties.
- The preferred polymer compositions within this range will depend largely on the properties desired. Generally, however, the polymers containing from 4 to 10% by weight of the methacrylate comonomer are preferred. This is because the heat distortion temperature, as is explained later, initially increases rapidly with methacrylate content to a broad peak between about 7 and 15% content and thereafter begins a gradual decline. Thus, roughly the same improvement is generally obtained at 7% as at 15% methacrylate content. Additionally, it is preferred to retain the thermal stability as high as possible so as to permit more flexibility in the application of forming processes to the polymers.
- The polymeric composition of the invention comprises a rubber substrate polymer having a glass transition temperature (Tg) below 0°C. grafted with a superstrate polymer and dispersed in a matrix polymer, the superstrate and the matrix polymers each comprising from 45 to 83% (preferably from 50 or 60 to 75%) by weight of a monoalkenyl aromatic monomer, from 15 to 35% (preferably 20-30%) by weight of an unsaturated dicarboxylic acid anhydride, and from 2 to 20% (preferably 4 to 10%) by weight of a C, to C3 alkyl methacrylate ester, the amount of rubber in the composition, calculated as ungrafted substrate, being from 2 to 30% of the composition weight.
- The rubber substrate component of the polymeric composition can be selected from a wide range of alternatives including butadiene polymers and copolymers, particularly the so-called "high-cis" diene rubbers which contain at least 90% by weight of cis-1,4-polybutadiene units, polyisoprene, polychloroprene, polyacrylate rubbers, and ethylene/propylene/diene rubbers (EPDM), polypentenamer and ethylene/vinyl acetate rubbers. Copolymers of cyclopentene with a minor proportion of a non-cyclic α olefin such as for example a copolymer of 55 to 95% of cyclopentene with from 5 to 45% of ethylene are also useful. Other rubbers which have a Tg below 0°C. and which may be grafted with the monomers used to produce the polymeric composition can readily be supplied by the skilled reader. The preferred rubbers have a Tg below about -30°C. and the most preferred are polybutadiene, particularly high-cis polybutadiene and copolymers of butadiene with up to 40% by weight of styrene or acrylonitrile comonomer.
- The monoalkenyl aromatic monomer is preferably styrene but styrene derivatives such as alphamethylstyrene, chlorostyrene, 2,4-dichlorostyrene and 2-chloro-4-methylstyrene may be substituted for styrene in whole or in part if desired.
- The unsaturated dicarboxylic acid anhydride is most preferably maleic anhydride though any of the homologues of mallic anhydride such as itaconic, citraconic and aconitic anhydrides can also be used.
- The polymeric composition further comprises a C, to C3 alkyl ester of methacrylic acid. The methacrylic ester can bp methyl methacrylate, ethyl methacrylate or propyl methacrylate. The preferred copolymerizable monomer is methyl methacrylate.
- The polymeric composition is conveniently prepared by dissolving the rubber in a solution of the monoalkenyl aromatic component and the methacrylate ester in a suitable solvent, and then polymerizing the solution with the anhydride component in the manner described in, for example, U.S.P. 2,971,939, U.S.P. 3,336,267 and U.S.P. 3,919,354.
- A suitable polymerization schedule can be devised on the basis of the relative reactivities of the monomers. Typical schedules involve preparing an initial reaction mixture comprising a solvent, the bulk of the alkenyl aromatic monomers, a very small amount (or none) of the anhydride monomer and the major proportion of the methacrylate termonomer. The rubber is dissolved in this mixture and the balance of the monomers is added slowly during the polymerization.
- The amount of rubber substrate (ungrafted basis) in the polymeric composition, which includes the grafted superstrate and any matrix polymer present, is in the range from 2 to 30% by weight based on the weight of the polymeric composition. Preferably, however, the rubber substrate represents from 5 to 25% of the weight of the polymeric composition.
- Since as has been indicated above, the addition of methyl methacrylate gives rise to reduction in the temperature at which thermal decomposition of the polymer begins, it is advantageous to incorporate an antioxidant stabilizer into the composition to provide an added degree of protection during processing.
- In protecting the polymer against thermal degradation, it is important from a practical point of view that the stability obtained has a reasonable duration. In the laboratory stability is often judged by the performance of the polymer in the molding of a small test-piece. In a commercial operation however, the polymer may well spend several minutes at molding temperatures and an acceptable polymer has to have stability not only at high temperatures but for prolonged periods at high temperatures.
- A wide range of antioxidant stabilizers for styrenic polymers is available but particularly satisfactory results can be obtained using 1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl]benzene and 2,2'-methylene-bis-(4-methyl-6-tert-butyl phenol)terethalate. The rubber component usually requires a different stabilizer such as a tris(alkylphenyl)phosphite though the prior art can supply others that would be effective.
- The total amount of stabilizer that may be used is not critical but up to 5% by weight based on the total composition is usually found to be adequate. In general 0.1 to 2% is the range chosen for practical advantage.
- The polymeric composition can contain other additives such as for example, additional ungrafted rubber components such as the so-called block rubbers and radial block rubbers, flame retardants, smoke suppressants, U.V. stabilizers, lubricants, antistatic additives, colorants and fillers.
- The effect of varying the methacrylate content of the terpolymer of the invention is graphically demonstrated by the drawing attached hereto.
- Figure 1 represents a graph plotting the change in DTUL with methacrylate content. The results plotted are those set forth in Example 9.
- The present invention is further described by reference to the following Examples which are for the purposes of illustration only and are not intended to imply any limitation of the scope of the invention.
- The polymer compositions are described on the basis of a combination of elemental analysis and titrimetric analysis techniques. The rubber concentration is determined on the basis of material balances in the polymer composition. Unless otherwise stated the rubber used was a medium-cis polybutadiene rubber available from Firestone Corp. under the trade name "Diene 55".
- The Examples illustrate the results of varying the amount of the methacrylate ester in the composition and the surprising advantages obtained by maintaining the level in the range of 2 to 20% by weight.
- In each Example the components were formed into samples which were then tested to determine the distortion temperature under load (DTUL) under a load of 18.6 kg/sq.cm. (ASTM D-648) and in some cases the Izod Impact Strength, (ASTM D-256) and/or the tensile strength or elongation at fail (ASTM D-638).
- In some Examples the multiaxial impact strength is shown. This is commonly called the F.D.I. and is measured according to ASTM D-1709 on a sample 2.9 mm in thickness.
- The Izod impact strengths were measured using 3.2x12.7x63.5 mm unannealed compression molded samples, notched 2.54 mm.
- The DTUL values given are for 3.2x12.7x127 mm unannealed compression molded samples tested under a 18.6 kg/sq.cm. stress.
- Unannealed compression molded samples were chosen in preference to injection molded samples so as to eliminate the variations that occur in the preparation of injection molded samples which become partially oriented during the forming process. The choice of unannealed compression molded samples which are not oriented during formation, eliminates, one result-affecting variable and makes the comparison more significant.
- These Examples describe the production of rubber-modified polymers of styrene, maleic anhydride and methyl methacrylate.
- The process described below is that used in Example 1 but essentially the same process was used in the other Examples with the difference that the initial monomer charge and the late added charge were changed in accordance with a computer model based on monomer reactivities to obtain polymers of different compositions. Typical late addition schedules of specified polymers predicted on the basis of the model are shown in Table 1.
- An agitated resin kettle was charged with 316 g. of styrene, 32.6 g. of methylmethacrylate, 0.5 g. of trisnonylphenyl phosphite (a stabilizer for the rubber) and a solvent mixture consisting of 50 g. of methyl ethyl ketone (MEK) and 75 g. of toluene. In this mixture were dissolved 44.2 g. of polybutadiene rubber.
- A solution of 0.6 g. of azobisisobutyronitrile (AIBN) and 3.2 g. of maleic anhydride in 30 ml. of MEK was prepared. 5 MI of this solution were added to the solution in the resin kettle and the rest was added at a rate of 3 ml/hour thereafter.
- The reaction mixture was raised to 85°C. and maintained at that level while late addition of a solution of 97 g. of maleic anhydride and 15 g. of methyl methacrylate in 97 g. of MEK was begun. The late addition was continued over a 6-1/2 hour period. After addition was complete the reaction was held at the reaction temperature for a further hour before 0.5 g. of hydroquinone was added to short-stop the reaction.
-
- In each case the amounts given are percentages by weight based on the total final polymer weight.
-
- The above results show that around 20% the DTUL improvement is substantially lost.
- These Examples illustrate the use of a different catalyst known to favor grafting in the production of a rubber-modified copolymer of styrene, maleic anhydride and methyl methacrylate and compare the result with a polymer containing no methyl methacrylate.
- The process described in Example 1 was followed except that the catalyst was changed from azobisisobutyronitrile to a mixture of tertiary butyl peroctoate and tertiary butyl peracetate. The results obtained are set forth in Table III below. Example 5 is for the sake of comparison and shows the results obtained in the absence of the methyl methacrylate component.
- Comparison of Examples 1 with 4 shows that using the peracetate catalyst it is possible to get comparable impact strengths while using a smaller amount of total rubber.
- Comparison of the RM-SMA with RM/S/MA/MMA shows the advantage of having the MMA present in terms both of DTUL, and percentage elongation at fail.
- This Example shows the advantages of RM-S/MA/MMA terpolymers over the corresponding RM-SMA polymers.
- The compositions compared were as follows:
- RM-SMA - 76/24-S/MA polymerized in the presence of 16.6% polybutadiene rubber. RM-S/MA/MMA―67/26/7―S/MA/MMA polymerized in the presence of 13.9% polybutadiene rubber.
- From these results it can be seen that distinct advantages in terms of physical properties are obtained by including methyl methacrylate as a termonomer in terms of heat distortion temperature, tensile strength and gloss of the final product.
- These Examples illustrate the use of a polypentenamer, (PP), a homopolymer of cyclopentene, to replace the polybutadiene used in the previous Examples.
- The compositions described in Table V below were made up using the following polymers.
- PPM-S/MA - A 75/25 SMA polymer polymerized in the presence of a polypentenamer using a mixture of tertiary butyl peracetate and tertiary butyl peroctoate as the catalyst/initiator.
- PPM-S/MA/MMA - A 66/25/9 S/MA/MMA polymerized in the presence of a polypentenamer using a mixture of tertiary butyl peracetate and tertiary butyl peroctoate as the catalyst/initiator.
-
- As can be seen from the above, the substitution of a cyclopentene homopolymer for polybutadiene produces very comparable results indicating that the effects shown do not depend on the use of polybutadiene.
- This Example sets forth the comparative data upon which Figure 1 is based.
- In each case the polymer was prepared in the manner described in Example 1 except for the addition of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene as antioxidant and the use of the catalyst combination of Example 4.
- The intention was to produce a series of polymers differing only in methyl methacrylate content and stryene content. In practice this is very difficult because the initial feed can only be roughly tailored to produce a desired composition without considerable trial and error testing.
- It has, however, been found that DTUL increases by 0.7°C. for each 1% decrease in the amount of rubber in the polymer and it increases 1.7°C. for every 1% rise in the proportion of maleic anhydride in the polymer.
-
- From the above Table VI it can be seen that around 15% methyl methacrylate a gradual decrease in DTUL begins. A graph of these (corrected) results appears in Figure 1.
- It can also be seen that although the effect is slightly distorted by a non-constant rubber level, the increasing methyl methacrylate content leads to a clear improvement in impact strength.
- This Example shows the decrease in temperature at which thermal degradation begins with the increase of the methyl methacrylate content.
- Polymers having the compositions described below were subjected to thermogravimetric analysis using a duPont Model 950 Thermogravimetric Analyzer. The heating rate used was 20°C. per minute. The "initial decomposition temperature" (IDT) was that at which 0.5% weight loss was observed.
- The compositions were tested: (A) without a stabilizer; (B) using '0.5% by weight of a 2,6-di- tertiary butyl- p-cresol stabilizer; and (C) using a mixture of 0.5% by weight of each of the stabilizer of (B) and 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.
-
- The results in Table VII show that the temperature at which the polymer begins to decompose decreases with increasing MMA content but that the choice of a suitable stabilizer can be very effective in controlling this trend below about 20% methyl methacrylate content.
- These Examples show the improvement obtained using a high-cis rubber, that is a polybutadiene containing over 90% of cis 1,4-polybutadiene units.
- The polymer used in Example 11 was prepared as follows:
- An agitated resin kettle was charged with 323 g. of styrene, 15 g. of methyl methacrylate, 0.1 g. of trisnonylphenyl phosphite (a stabilizer for the rubber) and a solvent mixture consisting of 50 g. of methyl ethyl ketone (MEK) and 75 g. of toluene. In this mixture were dissolved 54 g. of a high cis polybutadiene rubber. After the rubber was completely dissolved, a solution of 4 g. of maleic anhydride in 25 g. of MEK was added. The reaction mixture was raised to 85°C. and maintained at that level for the entire reaction period. One ml. of 75% solution of tertiary butyl peracetate in mineral spirit and 0.05 mi. of tertiary butyl peroctoate were added prior to late addition of a solution of 73 g. of maleic anhydride, and 7.3 g. of methyl methacrylate in 97.2 g. of MEK. The late addition was continued over a 6-1/2 hour period. Slug additions of 0.1 ml of t-butyl peroctoate were made at 1-1/2, 3, 4-1/2 hours during the late monomer addition. After addition was complete the reaction was held at the reaction temperature for a further 45 minutes before 0.5 g. of hydroquinone was added to short-stop the reaction.
- The polymer was then separated from the solvent and the residual monomer removed by a conventional method. The isolated polymer was blended with any desired additives, such as stabilizers, and compression molded into samples for evaluation.
- All the other polymers described in the Examples were prepared in essentially the same manner with the necessary adjustment to monomer and rubber charges being determined by the desired composition of the final polymer.
- The compositions contained 0.3% by weight of 1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl]benzene as an antioxidant stabilizer.
-
- Comparison of the Izod strengths with those given in Table VI shows that a very significant improvement in impact strength is obtained using this high-cis rubber. Surprisingly, the effect observed is greater where the polymer contains the methacrylate than where it does not.
- These Examples show the effect of the methyl methacrylate content of the polymer on its thermal stability.
- Polymers having the compositions given below were prepared using the method described in Example 12 with the necessary adjustments of monomer charge according to the computer schedule described in Example 1. No antioxidant stabilizer was used.
- Each sample was placed in the barrel of a capillary rheometer maintained at a constant temperature and extruded after a given residence time. The matrix phase of the polymer was separated from the grafted rubber phase and was analyzed for its maleic anhydride content by a standard titrimetric technique.
-
- As can readily be seen, the higher the proportion of MMA and the higher the temperature, the more readily does the decomposition of the polymer occur.
Tensile strength is measured by the method of ASTM D-638. Unannealed compression molded samples were 3.2x12.7x127 mm thickness samples. Gloss was assessed by visual inspection. Injection molded samples were 12.7 × 12.7 × 127 mm. The results are given in Table IV below.
Claims (3)
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US927429 | 1978-07-24 | ||
US05/927,429 US4341695A (en) | 1977-12-27 | 1978-07-24 | Rubber modified terpolymers with improved heat distortion resistance |
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EP0007931A1 EP0007931A1 (en) | 1980-02-20 |
EP0007931B1 true EP0007931B1 (en) | 1982-05-12 |
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EP78300909A Expired EP0007931B2 (en) | 1978-07-24 | 1978-12-27 | Rubber-modified terpolymers with improved heat distortion resistance |
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EP (1) | EP0007931B2 (en) |
JP (1) | JPS5518479A (en) |
AU (1) | AU520708B2 (en) |
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CA (1) | CA1121084A (en) |
DE (1) | DE2861838D1 (en) |
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JPS582313A (en) * | 1981-06-30 | 1983-01-07 | Daicel Chem Ind Ltd | Production of heat-resistant and impact-resistant resin |
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US2858281A (en) * | 1954-01-22 | 1958-10-28 | Goodrich Co B F | Insoluble, acid and alkali-resistant carboxylic polymers |
US3676526A (en) * | 1967-06-02 | 1972-07-11 | Eugene G Sommerfeld | Polymeric dispersion of a diene-acrylonitrite graft copolymer with a different graft copolymer |
CA882187A (en) * | 1968-03-13 | 1971-09-28 | Farbenfabriken Bayer Aktiengesellschaft | Thermoplastic-elastic moulding compounds |
US3919354A (en) * | 1972-09-08 | 1975-11-11 | Dow Chemical Co | Impact resistant polymers of a resinous copolymer of an alkenyl aromatic monomer and unsaturated dicarboxylic anhydride |
US3832274A (en) * | 1973-06-06 | 1974-08-27 | Lord Corp | Fast curing adhesives |
DE2329585C2 (en) * | 1973-06-09 | 1984-01-05 | Bayer Ag, 5090 Leverkusen | Polycarbonate molding compounds |
US3900528A (en) * | 1973-10-09 | 1975-08-19 | Monsanto Co | Process for impact modification of high nitrile polymers |
US3900529A (en) * | 1973-10-09 | 1975-08-19 | Monsanto Co | Rubber modified high nitrile polymers and polymer blends produced thereby |
IT1043117B (en) * | 1975-10-03 | 1980-02-20 | Snam Progetti | SHOCK RESINS AND METHOD FOR THEIR AREPARATION |
JPS52112692A (en) * | 1976-03-19 | 1977-09-21 | Toyo Soda Mfg Co Ltd | Method for carboxylation of ethylene-vinyl acetate copolymers |
US4097551A (en) * | 1976-12-20 | 1978-06-27 | Arco Polymers, Inc. | Rubber modified dicarboxylic acid copolymer blends |
-
1978
- 1978-12-26 BR BR7808510A patent/BR7808510A/en unknown
- 1978-12-26 JP JP16599478A patent/JPS5518479A/en active Granted
- 1978-12-27 EP EP78300909A patent/EP0007931B2/en not_active Expired
- 1978-12-27 IT IT31344/78A patent/IT1102788B/en active
- 1978-12-27 CA CA000318620A patent/CA1121084A/en not_active Expired
- 1978-12-27 DE DE7878300909T patent/DE2861838D1/en not_active Expired
- 1978-12-28 AU AU42921/78A patent/AU520708B2/en not_active Expired
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JPS5518479A (en) | 1980-02-08 |
AU4292178A (en) | 1980-01-31 |
IT7831344A0 (en) | 1978-12-27 |
DE2861838D1 (en) | 1982-07-01 |
EP0007931A1 (en) | 1980-02-20 |
MX150448A (en) | 1984-05-09 |
CA1121084A (en) | 1982-03-30 |
IT1102788B (en) | 1985-10-07 |
BR7808510A (en) | 1980-05-20 |
EP0007931B2 (en) | 1984-11-28 |
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